Process of preparing fulling liquors and emulsions



Patented June 4, 1929.

UNITED sr'rss PA E T orrics.

KARL DAIMLER, GERHABD BALLE, AND FRITZ JUST, or nocnsr ou-rnn-mam, ennmm, ASSIGNORS 'ro GBASSELLI DYESTUFF CORPORATION, or'nnw YORK, 11. m, A

' "ooR1=oRA'.r1oN or DELAWARE.

PROCESS OF PREPARING FULLING LIQUORS AND EMULSIONS.

No Drawing. Application filed January 28, 1926, Serial No. 84,498, and in Germany January 28, 1925.

The object of our present invention is the production of advantageous fulling liquors and emulsions particularly such as withstand the action of lime and acids, for which purpose we use sulfonic acids which exercise a no or an insufficiently tanning action but generally a more or less pronounced fatcleaving action. As is known preparations of this kind are preferably used for finishing animal textile material etc., such for instance as wool, silk, leather hides or the like.

The fulling liquors and emulsions obtainable according to our invention by means of the said sulfonic acids possess the great advantage over fulling liquors and emulsions of the ordinary kind, as previously prepared by means of soap, in that they do not give an alkaline reaction and that they can even be made acid without decomposition,' a fact which is of great importance in regard to the conservation of the animal textile goods and leather goods, because they stand a neutral or acid reaction much better than the generally weakly alkaline reaction of the ordinary falling liquors and emulsions prepared in the old manner by means of soap.

In the following description we describe the methods of using the said preparations.

In investigating the action of acid, neutral and also of alkaline fulling liquors we have ascertained that many sulfonic acids, which generally act more or less as fat-cleaving agents, and which ossess no tanning property at all or only in such insuflicient degree that they cannot be used for tanning purposes, are capable of accelerating the fulling action. Sulfonic acids of the said kind are readily soluble in neutral, alkaline, and acid solution so that they can be utilized when the fulling is carried out by means of an acid, or neutral, or also an alkaline fulling agent. They may be used either in their free state or in the form of salts; in both cases it is advantageous to incorporate the fulling agent into the wool to be fulled during the initial stage of the process, say during the softening operation together with the softening oil, which has been stabilized by means of the sulfonic acid. This renders the separate addition of the said agent to the fulling bat-h unnecessary, since the wool to be fulled it is the practice to ine washed and thereby render the fibre more supple and soft and I thereby facilitate the spinnin process. For

this purpose there are generally used no pure oils, but certain oil-soap-preparations, known under the names: softening, spinning, or spike oils. which may be bought ready made or specially prepared by the user himself, and which consists, for nstance of oils, such as olive oil mixed with a small quantity of soap or of oleic acid, mixed with a very small quantity of ammonia. When being used, these preparations are mixed and stirred with about two to four times the quantlty of water, whereby they are transformed into a kind of coarse emulsion. Such emul- SIOIIS, when allowed to stand, very soon separate into oil and soap water in consequence of the fact that, for certain reasons, their content of soap is generally kept extremely low so much so that this content of soap is insufficlent for a permanent emulsification, and therefore the said emulsions must be contin ually stirred or blown. Consequently it has been attempted to increase the stability of the emulsions by adding a protective colloid, such as a solution of ca'ragheen-moss or any other mucilaginous solution.

We have now found that in the preparation of emulsions of spinning oil the sulfonic acids above referred to and their salts are eminently suitable for being used as stabilizing agents (protective colloids) instead of mucilaginous substances, because their protestive power is much higher and, on the other hand, when drying they do not cause the formation of a hardening crust as does the said caragheen-moss. The useof the stabilizing agents to be employed according to our invention involves the further advantage that the oil emulsion penetrates much quicker into the wool to be softened and that the emulsion which dries after the material has been spun, is much more easily separated from the soapor soda-bath during the scouring proc- IOU ess than is the case when other protective colloids (caragheen-moss) or no such colloids at all are applied. The addition of the stabilizing agent may take place at any stage of the process, it may partlcularly be added to the undiluted softening oil as well as to the water serving as diluent and also to the completely diluted emulsion.

The above described favorable action of the sulfonic acids or their salts as they are to be used according to our invention as stabilizing agents, also suggests their use as emulsifying agents. Indeed, the products in question when in aqueous solution have to a great extent proved to be excellent emuL sifying agents. The concentrated aqueous solutions of many of these acids and salts, particularly the ammonium salt solutions, are capable of taking up large quantities of water-insoluble liquids, such as turpentine oil, decamphorated turpentine oil, benzene, tetraline, carbon tetrachloride, chlorobenzene or the like, with formation of homogeneous mostly clear mixtures which may be diluted, as desired, with water without destruction and which may be used for various purposes, particularly owing to their property of withstanding the action of acids.

The various classes of non-tanning or scarcely tanning but more or less fat-cleaving sulfonic acids to be used according to er invention may be subdivided into the folnuving four groups:

(1) Sulfonic acids of the benzene hydrocarbons (such as benzene, toluene, xylene, solvent naphtha, cymol, naphthalene, methylnaphthalene, tetraline, anthracene, phenanthrene) (2) Derivatives of these sulfonic acids substituted by cycloalkyl, aralkyl, aryl or fatty acid residues, and

(3) Derivatives of the said sulfonic acids substituted by alkyl and by cycloalkyl, aralkyl, aryl or fatty acid residues.

As representatives of these groups may be mentioned:

(1) cymolpolysulfonic acid, solvent naphtha sulfonic acid, tetralinepolysulfonic acid;

(2) cyelohexylnaphthalenesulfonic acid, eyclohexyltetraline sulfonic acid, benzylnaphthalenedisulfonic acid, benzylxylenesulfonic acid, phenylbenzenesulfonic acid; sul'tonic acid from naphthalene and talloil (a Swedish fluid resin left as waste in the sulfate-cellulose process) or naphthenic acid;

(3) cyclohexylbutylnaphthalenesulfonic acid; butylbenzyltoluenesulfonic acid; amylbenzylnaphthalenesulfonic acid; butylbenzyltetralinesulfonic acid; diethylbenzyltoluenesulfonic acid; isopropylbenzylnaphthalenesulfonic acid; butylphenylbenzenesulfonic acid; butylated sulfonic acid from naphthalene and tall-oil.

The fourth group comprises the sulfonic acids of the above groups 13 substituted in the nucleus or in the side chains by further As repfanihe acid; dimethylmethylidenenaphthalenesulfonic acid (obtained from acetone and naphthalenesulfonic acid).

As will be seen from the foregoing we expressly exclude from the class of non-tanning but fat-cleaving sulfonic acids described above, those sulfonic acids of hydrocarbons which are merely substituted in the nucleus by one or more alk 1 groups of at least 3 carbon atoms, such or instance as isopropylnaphthalenesulfonic acid or dibutylnaphthaleuesulfonic acid, as these acids are of an entirely soapy character and as their usefulness for the purpose claimed in'our application is obvious and already known.

In an analogous manner there may also be used instead of the above mentioned acids their salts. The term sulfonic acid compound as used in the claims annexed here-. to includes both the acid and salt derivatives of sulfonic acids.

Examples.

(1) One part by weight of the sulfonic acid obtained from 100 parts of naphthalene, 100 parts of cyclohexanol and 200 parts of chlorosulfonic acid are mixed with 10 parts of saponificate-oleine, one part of alcohol and one part of a solution of ammonia of 30% strength. For being used this softening oil which serves at the same time as fulling agent to be conveyed into the wool for the subsequent fulling process is emulsified in 4 times the quantity of water.

(2) 7 parts of commercial softening oil which may, for instance, be composed of 6 parts by weight of olive oil and one part of soap, are dissolved in 20 parts of water to which has been added one part of a protective colloid obtained in the following manner:

Into 100 parts of an oil, prepared from naphthalene and benzylchloride according to German Patent No. 416,904 is run, for effecting the sulfonation, a mixture of 25 parts of oleum (20%) and parts of chlorosulfonic acid, the mixture is then neutralized with caustic soda lye and after being dried and ground a yellowish-white powder which is readily soluble in water is obtained.

(3) The mixture serving as softening oil, composed of 10 parts of savonette-oil, one part of alcohol, one part of ammonia of 30% strength and 16 parts of softening oil is run into 100 parts of water, wherein one part of the product used according to Example 2 has been dissolved.

(4) An emulsifying oil, suitable for oiling tanned hides may be prepared from parts of alcohol, .20 parts of any of the sult'onio acids obtainable from naphthalene, benzylchloride, butylulcohol and a sull'tmating agent and 70 parts of train oil. This oil, when diluted with water, yields an emulsion, which may, for instance, be added to the vegetable tanning solution in the tanning cash towards the end of the tanning process.

3y adding small quantities of an alkali, such as sodium carbonate, ammonia etc. to the solvent-water the emulsion may also be rendered suitable for oiling chrom leather etc. after it has been tanned. Of course, there may also be introducedsodium carbonate, ammonia. alkali, pyridine into the already diluted oil or, instead of the free sulton ic acid and alcohol, aqueous concentrated solutions of the respective salt of the sulfonic acid may be mixed a priori with train oil. In the place of train oil there may also be used any other suitable oil- (5) An oil which yields in water a milky emulsion and which may be used for wetting and purifying purposes or for making dyestutl's into a paste etc. and for other purposes can be obtained by mixing parts of alcohol, parts of the sulfonic acid. used according to Example 1 and (50 parts of any substituent for turpentine oil, e. g. of the (lecan'iphorated turpentine oil produced in the iuanu'factureof artificial camphor. A mixture thus obtained yields on addition of water an emulsion of acid reaction which cannot be destroyed even by the addition of a mineral acid and which may for instance be employed in the wool industry for the most varied purposes. If this emulsion is neutralized with sodium carbonate, ammonia or pyridine etc. it may be used with great advantage in the cotton industry, as insecticide and as an admixture to substances for washing clothes.

\Ve claim:

1. The process of preparing fulling liquors and emulsions suitable for treating animal textile materials which comprises incorporating in the liquors a sult'onic acid of a compound of the group including the benzene and naphthalene series, said sulfonic acid being substituted by a substituent of the group including aryl, aralkyl, cyclo-alkyl and acyl.

2. The process of preparing fulling liquors and emulsions suitable for treating animal textile materials which comprises incorporating in the liquors a sulfonic acid of a compound of the group including the benzene and naphthalene series, said sulfonic acid being substituted by an alkyl group and a substituent of the group including aryl, aralkyl, yclo-alkyl, and acyl.

3. An emulsion suitable for treating wool which contains a softening oil, water, and a stal'iilizing agent comprising a sulfonic acid of a compound of the group including the benzene and naphthalene series, said sulfo'nic acid being substituted by asubstituent of the group including aryl, aralkyl, cycloalkyl, and acyl.

4 An. emulsion suitable for treating wool which contains a softening oil, water, and a stabilizing agent comprising a sulfonic acid of a compound of the group including the benzene and naphthalene series, said sull'ou ic acid being substituted by an alkyl group and a substituent of the group including aryl, aralkyl, cyclo-alkyl, and acyl.

In testimony whereof, we attix our signatures.

KARL DAIMLER. GERITA'RD BALLE. FRlTZ JUST. 

